UV‐ and thermally triggered ring‐opening metathesis polymerization for the spatially resolved functionalization of polymeric monolithic devices

Porous polymeric monolithic supports were prepared via electron beam‐triggered free radical polymerization using a mixture of ethyl methacrylate and trimethylolpropane triacrylate in 2‐propanol, 1‐dodecanol and toluene. Bicyclo[2.2.1]hept‐5‐en‐2‐ylmethyl acrylate (1) was grafted onto these monolithic supports in a spatially resolved way with the aid of masks using both electron beam‐ (EB) and UV‐triggered free radical polymerization. The thus immobilized norborn‐2‐ene‐containing graft polymers were further treated with the 2 nd ‐generation Grubbs initiator, i.e., RuCl 2 (PCy 3 )(IMesH 2 )(CHPh) (4) (IMesH 2 = 1,3‐dimesitylimidazolin‐2‐ylidene), and then reacted with bicyclo[2.2.1]hept‐5‐en‐2‐ylmethyl pyrene‐1‐carboxylate (2). Alternatively, monoliths completely grafted with poly‐ 1 were surface grafted with 2 in a spatially resolved way in the presence of a latent, UV‐triggerable precatalyst, i.e., [Ru(IMesH 2 )(CF 3 COO)( t ‐BuCN) 4 + CF 3 COO − ] (5). Finally, to demonstrate the utility of this chemistry, a 2 nd ‐generation Grubbs initiator‐based approach was used to prepare a trypsin‐functionalized monolith‐containing chip device that allowed for the online digestion of N ‐α‐benzoyl‐ L ‐argininethylester hydrochloride. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011